1. Field of the Invention
Embodiments of the present invention relate to a method for producing stoichiometric LiMn2O4, the material produced thereby, a cathode formed from the material and a battery containing the cathode. The invention also relates to a stoichiometric LiMn2O4 arranged into a structure comprising fused particles, a cathode formed from the material and a battery containing the cathode. In further embodiments, the invention relates to a method for producing a material having the formula Li[Ni0.5Mn1.5]O4-δ wherein δ≧O. In further embodiments, the invention relates to a material having the formula Li[Ni0.5Mn1.5]O4-δ wherein δ≧O, arranged into a structure comprising fused particles, the material produced thereby, a cathode formed from the material and a battery containing the cathode.
2. Description of the Related Art
Future rechargeable lithium batteries require lithium intercalation cathodes that combine low cost, low toxicity, and high safety with high rates of intercalation/deintercalation. The lithium intercalation compounds LiFePO4 olivine and LiMn2O4 spinel have received particular attention in this regard. The latter has been studied as an intercalation electrode for many years and exhibits a potential of 4 V versus Li+(1 M)/Li when cycled over the composition range of LixMn2O4, 0<×<1. Early work soon identified that stoichiometric LiMn2O4 shows considerable capacity fading on cycling, associated with structural degradation, and poor rate performance. As a result, attention turned to nonstoichiometric spinels such as Li1.05Mn1.95O4, which demonstrate better cycling stability despite lower theoretical and practical capacities due to a Mn valence >3.5. These materials failed to show sufficient stability on cycling at elevated temperatures (150° C.) resulting in the study of even less stoichiometric compositions, i.e., more Li-rich further compromising capacity, doping with foreign ions (e.g., F-, transition metals), application of coatings (e.g., ZnO, LiCoO2), or utilization of electrolyte additives or different electrolytes.
In addition, to achieve the goal of new rechargeable lithium batteries for new markets, there is interest in moving the electrochemical window within which such devices operate from the present 0 to 3.5-4.0 V versus Li+(1 M)/Li to 1 to 1.5-5 V versus Li+(1 M)/Li, primarily for reasons of safety and overcharge protection. This involves replacing the current negative and positive electrode materials, graphite and LiCoO2, respectively, with new lithium intercalation materials operating satisfactorily in the higher voltage regime. For the negative electrode, titanates are favoured e.g., the spinel Li4Ti5O12 or TiO2—(B) (˜1.5 V versus Li+(1 M)/Li). The Li[Ni0.5Mn1.5]O4 spinel is one of the most promising candidates as the positive electrode. It exhibits stable intercalation-deintercaltion of lithium at ˜4.7 V versus Li+(1 M)/Li.
Background information relating to LiMn2O4 can be found in the following sources; some of these references are referred to in Tables 1 and 2:    (1) Padhi, A. K.; Nanjundaswamy, K. S.; Goodenough, J. B. J. Electrochem. Soc. 1997, 144, 1188.    (2) (a) a Thackeray, M. M.; Johnson, P. J.; Depicciotto, L. A.; Bruce, P. G.; Goodenough, J. B. Mater. Res. Bull. 1984, 19, 179. (b) Thackeray, M. M. Prog. Solid State Chem. 1997, 25, 1. (c) Tarascon, J. M.; Guyomard, D. J. Electrochem. Soc. 1991, 138, 2864.    (3) (a) a Pasquier, A. D.; Blyr, A.; Courjal, P.; Larcher, D.; Amatucci, G.; Gerand, B.; Tarascon, J. M. J. Electrochem. Soc. 1999, 146, 428. (b) Amatucci, G.; Tarascon, J. M. J. Electrochem. Soc. 2002, 149, K31. (c) Huang, H.; Vincent, C. A.; Bruce, P. G. J. Electrochem. Soc. 1999, 146, 3649. (d) Shin, Y.; Manthiram, A. J. Electrochem. Soc. 2004, 151, A204.    (4) (a) Cho, J.; Thackeray, M. M. J. Electrochem. Soc. 1999, 146, 3577. (b) Xia, Y.; Sakai, T.; Fujieda, T.; Yang, X. Q.; Sun, X.; Ma, Z. F.; McBreen, J.; Yoshio, M. J. Electrochem. Soc. 2001, 148, A723. (c) Takada, T.; Hayakawa, H.; Enoki, H.; Akiba, E.; Slegr, H.; Davidson, I.; Murray, J. J. Power Sources 1999, 81-82, 505. (d) Thackeray, M. M.; Yang, S. H.; Kahaian, A. J.; Kepler, K. D.; Skinner, E.; Vaughey, J. T.; Hackney, S. A. Electrochem. Solid-State Lett. 1998, 1, 7.    (5) Xia, Y.; Zhou, Y.; Yoshio, M. J. Electrochem. Soc. 1997, 144, 2593.    (6) Amatucci, G. G.; Pereira, N.; Zheng, T.; Tarascon, J. M. J. Electrochem. Soc. 2001, 148, A171.    (7) Larcher, D.; Gerand, B.; Tarascon, J. M. J. Solid State Electrochem. 1998, 2, 137.    (8) Shin, Y.; Manthiram, A. Chem. Mater. 2003, 15, 2954.    (9) Kannan, A. M.; Manthiram, A. Electrochem. Solid-State Lett. 2002, 5, A167.    (10) (a) Song, D.; Ikuta, H.; Uchida, T.; Wakihara, M. Solid State Ionics 1999, 117, 151. (b) Shaju, K. M.; Subba Rao, G. V.; Chowdari, B. V. R. Solid State Ionics 2002, 148, 343. (c) Okada, M.; Lee, Y.-S.; Yoshio, M. J. Power Sources 2000, 90, 196.    (11) Sun, Y. K.; Hong, K. J.; Prakash, J. J. Electrochem. Soc. 2003, 150, A970.    (12) Liu, H.; Cheng, C.; Zongqiuhu; Zhang, K. Mater. Chem. Phys. 2007, 101, 276.    (13) Li, C.; Zhang, H. P.; Fu, L. J.; Liu, H.; Wu, Y. P.; Rahm, E.; Holze, R.; Wu, H. Q. Electrochim. Acta 2006, 51, 3872.    (14) (a) Chen, Z.; Lu, W. Q.; Liu, J.; Amine, K. Electrochim. Acta 2006, 51, 3322. (b) Zhang, S. S.; Xu, K.; Jow, T. R. J. Power Sources 2006, 154, 276. (c) Yu, B. T.; Qiu, W. H.; Li, F. S.; Cheng, L. J. Power Sources 2007, 166, 499.    (15) (a) Shaju, K. M.; Bruce, P. G. AdV. Mater. 2006, 18, 2330. (b) Shaju, K. M.; Bruce, P. G. J. Power Sources 2007, 174, 1201.    (16) Kim, J. S.; Johnson, C. S.; Vaughey, J. T.; Hackney, S. A.; Walz, K. A.; Zeltner, W. A.; Anderson, M. A.; Thackeray, M. M. J. Electrochem. Soc. 2004, 151, A1755.    (17) Jiang, C. H.; Dou, S. X.; Liu, H. K.; Ichihara, M.; Zhou, H. S. J. Power Sources 2007, 172, 410.    (18) Zhang, Y.; Shin, H. C.; Dong, J.; Liu, M. Solid State Ionics 2004, 171, 25.    (19) Huang, S.; Wen, Z.; Yang, X.; Zhu, X.; Lin, B. Electrochem. Solid-State Lett. 2006, 9, A443.    (20) Luo, J.; Cheng, L.; Xia, Y. Electrochem. Commun. 2007, 9, 1404.    (21) Park, S. C.; Han, Y. S.; Kang, Y. S.; Lee, P. S.; Ahn, S.; Lee, H. M.; Lee, J. Y. J. Electrochem. Soc. 2001, 148, A680.    (22) Lanz, M.; Kormann, C.; Steininger, H.; Heil, G.; Haas, O.; Novak, P. J. Electrochem. Soc. 2000, 147, 3997.    (23) Wang, X.; Tanaike, O.; Kodama, M.; Hatpri, H. J. Power Sources 2007, 168, 282.    (24) Chiu, K. F.; Lin, H. C.; Lin, K. M.; Chen, C. C. J. Electrochem. Soc. 2006, 153, A1992.    (25) (a) Blyr, A.; Sigala, C.; Amatucci, G.; Guyomard, D.; Chabre, Y.; Tarascon, J. M. J. Electrochem. Soc. 1998, 145, 194. (b) Sun, Y. K.; Yoon, C. S.; Kim, C. K.; Youn, S. G.; Lee, Y. S.; Yoshio, M.; Oh, I. H. J. Mater. Chem. 2001, 11, 2519.    (26) (a) Aurbach, D.; Markovsky, B.; Levi, M. D.; Levi, E.; Schechter, A.; Moshkovich, M.; Cohen, Y. J. Power Sources 1999, 81-82, 95. (b) Aurbach, D.; Gamolsky, K.; Markovsky, B.; Salitra, G.; Gofer, Y.; Heider, U.; Oesten, R.; Schmidt, M. J. Electrochem. Soc. 2000, 147, 1322.    (27) (a) Mohamedi, M.; Takahashi, D.; Uchiyama, T.; Itoh, T.; Nishizawa, M.; Uchida, I. J. Power Sources 2001, 93, 93. (b) Shaju, K. M.; Subba Rao, G. V.; Chowdari, B. V. R. J. Mater. Chem. 2003, 13, 106. (c) Dokko, K.; Mohamedi, M.; Umeda, M.; Uchida, I. J. Electrochem. Soc. 2003, 150, A425.    (28) (a) Thomas, M. G. S. R.; Bruce, P. G.; Goodenough, J. B. J. Electrochem. Soc. 1985, 132, 1521. (b) Conway, B. E. J. Electrochem. Soc. 1991, 138, 1539. (c) Choi, Y. M.; Pyun, S. I.; Bae, J. S.; Moon, S. I. J. Power Sources 1995, 56, 25.    (29) (a) Edstrom, K.; Gustafsson, T.; Thomas, J. O. Electrochim. Acta 2004, 50, 397. (b) Eriksson, T.; Gustafsson, T.; Thomas, J. O. Electrochem. Solid-State Lett. 2002, 5, A35.    (30) Tronel, F.; Guerlou-Demourgues, L.; Menetrier, M.; Croguennec, L.; Goubault, L.; Bernard, P.; Delmas, C. Chem. Mater. 2006, 18, 5840.
Background information relating to Li[Ni0.5Mn1.5]O4 can be found in the following sources; some of these references are referred to herein by recitation of the number of the reference in superscripted font:    (1*) K. Ariyoshi and T. Ohzuku, J. Power Sources, 2007, 174, 1258.    (2*) K. Ariyoshi, R. Yamato, Y. Makimura, T. Amazutsumi, Y. Maeda and T. Ohzuku, Electrochemistry, 2008, 76, 46.    (3*) P. G. Bruce, B. Scrosati and J. M. Tarascon, Angew. Chem., Int. Ed., 2008, 47, 2930.    (4*) Q. M. Zhong, A. Bonakdarpour, M. J. Zhang, Y. Gao and J. R. Dahn, J. Electrochem. Soc., 1997, 144, 205.    (5*) K. Amine, H. Tukamoto, H. Yasuda and Y. Fujita, J. Power Sources, 1997, 68, 604.    (6*) J. M. Tarascon, E. Wang, F. K. Shokoohi, W. R. McKinnon and S. Colson, J. Electrochem. Soc., 1991, 138, 2859.    (7*) H. Kawai, M. Nagata, H. Tukamoto and A. R. West, J. Power Sources, 1999, 81-82, 67.    (8*) T. Ohzuku, S. Takeda and M. Iwanaga, J. Power Sources, 1999, 81-82, 90.    (9*) M. Kunduraci, J. F. Al-Sharab and G. G. Amatucci, Chem. Mater., 2006, 18, 3585.    (10*) J.-H. Kim, S.-T. Myung, C. S. Yoon, S. G. Kang and Y.-K. Sun, Chem. Mater., 2004, 16, 906.    (11*) S.-H. Park and Y.-K. Sun, Electrochim. Acta, 2004, 50, 431.    (12*) K. Ariyoshi, Y. Iwakoshi, N. Nakayama and T. Ohzuku, J. Electrochem. Soc., 2004, 151, A296.    (13*) K. Takahashi, M. Saitoh, M. Sano, M. Fujita and K. Kifune, J. Electrochem. Soc., 2004, 151, A173.    (14*) F. G. B. Ooms, M. Wagemaker, A. A. Van Well, F. M. Mulder, E. M. Kelder and J. Schoonman, Appl Phys. A, 2002, 74, S1089.    (15*) M. Kunduraci and G. G. Amatucci, J. Electrochem. Soc., 2006, 153, A1345.    (16*) Y. Idemoto, H. Narai and N. Koura, J. Power Sources, 2003, 119-121, 125.    (17*) S. H. Park, S. W. Oh, S. H. Kang, I. Belharouak, K. Amine and Y. K. Sun, Electrochim. Acta, 2007, 52, 7226.    (18*) J. H. Kim, C. S. Yoon, S. T. Myung, J. Prakash and Y. K. Sun, Electrochem. Solid-State Lett., 2004, 7, A216.    (19*) R. Alcantara, M. Jaraba, P. Lavela, J. L. Tirado, E. Zhecheva and R. Stoyanova, Chem. Mater., 2004, 16, 1573.    (20*) H. Fang, Z. Wang, B. Zhang, X. Li and G. Li, Electrochem. Commun., 2007, 9, 1077.    (21*) D. Pasero, N. Reeves, V. Pralong and A. R. West, J. Electrochem. Soc., 2008, 155, A282.    (22*) L. J. Fu, H. Liu, C. Li, Y. P. Wu, E. Rahm, R. Holze and H. Q. Wu, Prog. Mater. Sci., 2005, 50, 881.    (23)* Y.-K. Sun, Y.-S. Lee, M. Yoshio and K. Amine, Electrochem. Solid-State Lett., 2002, 5, A99.    (24*) Y. Talyosef, B. Markovsky, R. Lavi, G. Salitra, D. Aurbach, D. Kovacheva, M. Gorova, E. Zhecheva and R. Stoyanova, J. Electrochem. Soc., 2007, 154, A682.    (25*) M. G. Lazarraga, L. Pascual, H. Gadjov, D. Kovacheva, K. Petrov, J. M. Amarilla, R. M. Rojas, M. A. Martin-Luengo and J. M. Rojo, J. Mater. Chem., 2004, 14, 1640.    (26*) J. C. Arrebola, A. Caballero, M. Cruz, L. Hernan, J. Morales and E. R. Castellon, Adv. Funct. Mater., 2006, 16, 1904.    (27*) R. Alcantra, M. Jaraba, P. Lavela and J. L. Tirado, J. Electroanal. Chem., 2004, 566, 187.    (28*) D. Aurbach, B. Markovsky, Y. Talyossef, G. Salitra, H.-J. Kim and S. Choi, J. Power Sources, 2006, 162, 780.    (29*) S. H. Oh, S. H. Jeon, W. I. cho, C. S. Kim and B. W. Cho, J. Alloys Compd., 2008, 452, 389.    (30*) L. Xiao, Y. Zhao, Y. Yang, X. Ai, H. Yang and Y. Cao, J. Solid State Electrochem., 2008, 12, 687.    (31*) J. C. Arrebola, A. Caballero, L. Hernan and J. Morales, J. Power Sources, 2008, 180, 852.    (32*) K. M. Shaju and P. G. Bruce, Adv. Mater., 2006, 18, 2330.    (33*) K. M. Shaju and P. G. Bruce, J. Power Sources, 2007, 174, 1201.    (34*) H. Fang, L. Li and G. Li, J. Power Sources, 2007, 167, 223.    (35*) S. Patoux, L. Sannier, H. Lignier, Y. Reynier, C. Bourbon, S. Jouanneau, F. L. Cras and S. Martinet, Electrochim. Acta, 2008, 53, 4137.    (36*) T. A. Arunkumar and A. Manthiram, Electrochem. Solid-State Lett., 2005, 8, A403.    (37*) H. M. Wu, J. P. Tu, Y. F. Yuan, Y. Li, X. B. Zhao and G. S. Cao, Electrochemim. Acta, 2005, 50, 4104.    (38*) D. Li, A. Ito, K. Kobayakawa, H. Noguchi and Y. Sato, Electrochim. Acta, 2007, 52, 1919.    (39*) D. Aurbach, M. D. Levi, K. Gamulski, B. Markovsky, G. Salitra, E. Levi, U. Heider, L. Heider and R. Oesten, J. Power Sources, 1999, 81-82, 472.    (40*) K. M. Shaju, G. V. SubbaRao and B. V. R. Chowdari, J. Mater. Chem., 2003, 13, 106.    (41*) M. Mohamedi, D. Takahashi, T. Uchiyama, T. Itoh, M. Nishizawa and I. Uchida, J. Power Sources, 2001, 93, 93.